Calculation Of Equilibrium Composition Research Articles

Calculation of Decomposition Products from Components of Gunpowder by using ReaxFF Reactive Force Field Molecular Dynamics and Thermodynamic Calculations of Equilibrium Composition

AbstractThe major combustion products from munitions containing nitro‐based propellants are water, carbon monoxide, carbon dioxide, hydrogen, and nitrogen. In addition, compounds including hydrogen cyanide, ammonia, methane, nitrogen oxides, benzene, acrylonitrile, toluene, furan, aromatic amines, benzopyrene, and various polycyclic aromatic hydrocarbons are detected in minor concentrations. The literature shows that the thermodynamic prediction of the major decomposition products agrees fairly well with the measurements. However, poor agreement is found for the minor species. We have studied the thermal decomposition products of the main gunpowder ingredients. Each of the components nitrocellulose, nitroglycerine, and the nitrate ester stabilizers diphenylamine and ethyl centralite were thermally decomposed with ReaxFF reactive force field molecular dynamics and equilibrium thermodynamics. The molecular dynamics results for the major decomposition products from nitrocellulose were partly consistent with measurements. Compared to the thermodynamic calculations, the molecular dynamics simulations agreed considerably better with experimental results for minor species like hydrogen cyanide. The nitrate ester stabilizers are the main sources for ammonia and aromatic combustion products, whereas hydrogen cyanide is produced from nitrocellulose as well as from the stabilizers when gunpowder is combusted.

Catalytic aromatization of methane

Recent developments in natural gas production technology have led to lower prices for methane and renewed interest in converting methane to higher value products. Processes such as those based on syngas from methane reforming are being investigated. Another option is methane aromatization, which produces benzene and hydrogen: 6CH4(g) → C6H6(g) + 9H2(g) ΔG°(r) = +433 kJ mol(-1) ΔH°(r) = +531 kJ mol(-1). Thermodynamic calculations for this reaction show that benzene formation is insignificant below ∼600 °C, and that the formation of solid carbon [C(s)] is thermodynamically favored at temperatures above ∼300 °C. Benzene formation is insignificant at all temperatures up to 1000 °C when C(s) is included in the calculation of equilibrium composition. Interestingly, the thermodynamic limitation on benzene formation can be minimized by the addition of alkanes/alkenes to the methane feed. By far the most widely studied catalysts for this reaction are Mo/HZSM-5 and Mo/MCM-22. Benzene selectivities are generally between 60 and 80% at methane conversions of ∼10%, corresponding to net benzene yields of less than 10%. Major byproducts include lower molecular weight hydrocarbons and higher molecular weight substituted aromatics. However, carbon formation is inevitable, but the experimental findings show this can be kinetically limited by the use of H2 or oxidants in the feed, including CO2 or steam. A number of reactor configurations involving regeneration of the carbon-containing catalyst have been developed with the goal of minimizing the cost of regeneration of the catalyst once deactivated by carbon deposition. In this tutorial review we discuss the thermodynamics of this process, the catalysts used and the potential reactor configurations that can be applied.

Thermodynamic Analysis of the Cu-As-S-(O) System Relevant to Sulfuric Acid Baking of Enargite at 473 K (200 °C)

While the growing demand for copper has compelled the industry to adapt new technologies for the treatment of copper-arsenic (enargite) concentrates, the refractory nature of such concentrates combined with the troublesome presence of arsenic has created a major metallurgical and environmental challenge. Preliminary results of the acid bake-leach process at the University of Utah have shown some potential advantages for the treatment of enargite concentrates. While the transformation of enargite to copper sulfate, arsenolite, and elemental sulfur has already been established experimentally, thermodynamic evaluation of the sulfuric acid baking process provides further understanding which should be useful. In this article, the available thermodynamic data for the species involved in the Cu-As-S-O system are compiled. These data were used to calculate the phase stability (Kellogg) diagrams as well as equilibrium compositions at 473 K (200 °C) using the STABCAL and HSC Chemistry® 5.1 software packages. The equilibrium composition calculations indicate that enargite can transform to copper sulfate either directly or through chalcocite and/or covellite. The major gaseous species during baking were found to be SO2 and H2O. The results of the thermodynamic calculations were further compared with two confirmatory baking experiments involving a high-quality enargite sample. The condensed reaction products from sulfuric acid baking based on XRD results include CuSO4, As2O3, CuO·CuSO4, and S8 under both neutral and oxidative conditions. While all these compounds were predicted through equilibrium calculations, some of the predicted compounds were not detected in the sulfuric acid-baked enargite. None of the calculations indicated any appreciable amounts of arsenic-bearing gases at the baking temperature of 473 K (200 °C). Consistent with thermodynamic predictions, no H2S gas was detected during the sulfuric acid baking experiment. Approximately, 80 pct of the baked enargite samples were leached in water.

Solubilities of some gases in four immidazolium-based ionic liquids

The synthetic-volumetric method is used for rapidly measuring solubilities of sparingly-soluble gases in monoethylene glycol and in four ionic liquids. Known molar quantities of solute and solvent are charged into an equilibrium vessel. Measured quantities at equilibrium include: temperature, pressure, quantities of fluids, and volumes of the gas and liquid phases in the equilibrium vessel. These measurements enable calculation of equilibrium compositions using material balances. No sampling or chemical analyses are required.Solubilities are reported for carbon dioxide, krypton, oxygen, and hydrogen in monoethylene glycol, l-n-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4], l-n-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][Tf2N], or 1-ethyl-3-methylimidazolium acetate [EMIM][AC]. Solubilities were measured over the temperature range (298 to 355)K and for pressures up to about 7MPa using two different pieces of equipment, both based on the volumetric method: a low-pressure glass apparatus and a high-pressure stainless-steel apparatus. Special emphasis is given to experimental reliability to assure consistent data.

Interaction Between Eutectic Intermetallic Particles and Dispersoids in the 3003 Aluminum Alloy During Homogenization Treatments

The transformation of primary eutectic Al6(Mn,Fe) intermetallics into α-Al(Mn,Fe)Si and the precipitation of dispersoids were studied in the commercial in the form of 3003 series cast aluminum alloys, mainly under isothermal conditions between 673 K and 873 K (400 °C and 600 °C). After solidification, both the solid solution and the primary eutectic intermetallics were far from equilibrium. During further heat treatment, the precipitation of fine dispersoids and eutectoid transformation of the primary eutectic particles occurred simultaneously. Having characterized these evolutions under industrial homogenization conditions, the evolution of the microstructure (in terms of its nature, and the quantity, size, and chemical composition of the phases) was characterized during isothermal heat treatment, using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations, quantitative image analysis, and transmission electron microscopy–energy-dispersive spectroscopy (TEM-EDS). The experimental results are analyzed, and changes in chemical composition are discussed and compared with the calculated equilibrium compositions. It is shown that (1) the chemical composition of eutectic intermetallics evolves and tends toward an equilibrium composition; (2) during precipitation, the chemical composition of dispersoids is constant, and close to the expected equilibrium composition when the initial mean composition of the solidification cell is taken into account; (3) after the formation of dispersoids, the quantity of α-Al(Mn,Fe)Si formed from the initial eutectic intermetallics increased, with the kinetics being controlled by long-range manganese diffusion; and (4) the latter evolution is associated with the dissolution of dispersoids located close to eutectic intermetallics and contributes to the formation of a dispersoid-free zone (DFZ).

Transport properties of CF3I thermal plasmas mixed with CO2, air or N2 as an alternative to SF6 plasmas in high-voltage circuit breakers

This paper is devoted to the calculation of equilibrium compositions, thermodynamic properties (mass density, enthalpy and specific heat at constant pressure) and transport coefficients (viscosity, electrical conductivity and thermal conductivity) of air/CO2/N2–CF3I mixtures. These data are computed in the temperature range 300 K–50 kK and pressure between 1 and 32 bar. Results obtained for pure gases (CF3I, CO2, air and N2) are systematically compared with SF6. Transport coefficients for N2, CO2, CF3I and mixtures of CO2, N2 or air with CF3I are also confronted with previous published values. Particular attention is paid to the collision integral database by the use of the most accurate and recent cross-sections or interaction potentials available in the literature.

Kinetics of silver anodic dissolution in thiosulfate electrolytes

The regularities of silver anodic dissolution are studied by using the voltammetry (at the potential scan rates from 5 to 1000 mV/s) on the electrode, which was renewed immediately in the solution by cutting-off a thin surface metal layer, and quartz microgravimetry, for various concentrations of sodium thiosulfate (0.05–0.2 M). It is shown that, in the potential range from 0 to 0.4 V (normal hydrogen electrode), the polarization curves reflect the silver dissolution, whereas the contribution of oxidation of S2O 3 2− ions is insignificant. At low potential scan rates, the process kinetics is of mixed nature. The kinetics and mechanism of anodic process are studied by using the measurements at high potential scan rates (100–200 mV/s) and the calculations of equilibrium composition of near-electrode layer. It is found that the exchange current in the electrolytes studied is 5 × 10−5 A/cm2, the transfer coefficient α is approximately 0.5, and both parameters are virtually independent of the concentration of S2O 3 2− ions. The reaction order of silver dissolution with respect to the ligand \( \left. {\frac{{\partial logi}} {{\partial logc}}} \right|_E \) is close to unity and is independent of potential. With regard for the literature data on the adsorption of thiosulfate ions on silver, this result is interpreted as the evidence for the involvement of one S2O 3 2− ion from bulk solution, along with adsorbed ligands, in the elementary act of metal dissolution.

Temperature and Electron Density Measurements of Laser-Induced Plasmas in Air at Elevated Pressures

ABSTRACT We present time-resolved spectroscopic measurements of 1064-nm Nd:YAG laser-produced plasmas in air at pressures from 0.85 to 48.3 bar. We report temperatures and electron number densities of the plasmas at times between 200 ns and 3 µs after the plasma onset. Neutral atomic oxygen lines at 715 nm and 777 nm are used for temperature measurement through a Boltzmann analysis. Electron number density is measured using Stark broadened atomic hydrogen (Hα) line at 656 nm. We compare experimental results with modeling results obtained from using Taylor-Sedov blast-wave theory coupled with local thermal equilibrium composition calculations.

LLE for (water + ionic liquid) binary systems using [C xmim][BF 4] ( x = 6, 8) ionic liquids

Liquid–liquid equilibrium diagrams were determined for (IL + water) systems using the family of ILs 1-alkyl-3-methylimidazolium tetrafluoroborates, where the alkyl groups are hexyl and octyl ([C x mim][BF 4] with x = 6 and 8). The gravimetric method was used to determine the equilibrium compositions at temperatures ranging from 278.15 to 340.15 K. Both systems present an upper critical solution temperature (UCST), which increases from [C 6mim][BF 4] to [C 8mim][BF 4]. The experimental data were correlated using the NRTL and eNRTL models. The binary interaction parameters were calculated for each system and model, and good agreement between experimental and calculated equilibrium compositions was obtained. Finally, the apparent Gibbs energy, enthalpy and entropy of water solution in the ILs were calculated using a modified van’t Hoff equation. The three thermodynamic functions were found to be positive for both ILs.

Calculation of mixture equilibrium binary interaction parameters using closed cup flash point measurements

Proper design and operation of separation processes are highly dependent on phase equilibrium calculations. The common method to treat polar/nonpolar systems, and also mixtures of normal compounds where the sizes are significantly different is to use binary interaction parameters. This paper presents a method to calculate mixture binary interaction parameters using closed cup flash point measurements. The measured and literature closed cup flash points of different binary mixtures (ethanol + n-octane, 1-propanol + n-octane, 1-propanol + n-decane, n-octane + n-decane, 1-propanol + water, 1-butanol + n-octane, 2-butanol + n-octane, and water + propionic acid) are used to calculate binary interaction parameters. These binary interaction parameters together with common activity models are then used to calculate vapor–liquid equilibrium compositions of different binary mixtures considered in this study. The validity of the proposed method was successfully approved by comparing the calculated equilibrium compositions with experimental data.

Calculation of Equilibrium Compositions of Systems of Enzyme-Catalyzed Reactions

When a system of enzyme-catalyzed reactions does not involve H(2)O as a reactant, the equilibrium composition at specified temperature, pH, and ionic strength can be calculated using the Mathematica programs equcalcc, which uses the conservation matrix, or equcalcrx, which uses the stoichiometric number matrix. When H(2)O is involved as a reactant, equcalcrx must be used because H(2)O is not in the stoichiometric number matrix. It is shown here that the use of equcalcrx is equivalent to using the further transformed Gibbs energy G" that eliminates oxygen from the conservation matrix. Calculations presented here show that the calculation of further transformed Gibbs energies of formation of reactants other than coenzymes can be avoided by using equcalcrx to calculate equilibrium concentrations.

Rocket Propellant Characteristics of Silanes/O2

We present a theoretical analysis of the applicability of various silicon hydrides (silanes) as rocket propellants. Thermodynamic data sets for 12 different silanes ranging from monosilane SiH4 to pentasilane Si5H12 were generated based on existing data. They were derived from empirically corrected thermochemical ab initio calculations and used in conjunction with the well-known computer packages NASA CEA2 and CHEMKIN to calculate equilibrium compositions and rocket performance indices. The thermodynamic datasets are now publicly available online for future calculations. Chemical equilibrium combustion compositions and adiabatic flame temperatures in rocket combustion chambers and the specific impulses at the nozzle exit assuming shifting equilibrium were calculated for several silane fuels using oxygen as oxidizer. The computational results created by CEA2 and CHEMKIN are in very good agreement to each other and are compared to conventional fuels such as liquid hydrogen (LH), hydrocarbons and hydrazines. Compared to alkane fuels, the combustion of silanes with oxygen-despite the much higher average molecular mass of the combustion products-results in similar maximum specific impulses and adiabatic flame temperatures due to the high positive values of the heats of formation of the silanes, indicating that silanes may be interesting candidates as rocket propulsion fuels.

Isobaric (vapor + liquid) equilibria of the binary system maleic anhydride and diethyl phthalate at p = (2.67, 5.33, and 8.00) kPa

Saturated vapor pressures of pure diethyl phthalate were measured with the ebulliometer. And isobaric (vapor + liquid) equilibrium data for the binary system (maleic anhydride + diethyl phthalate) at p = (2.67, 5.33, and 8.00) kPa were determined using the ebulliometric method. The parameters of the NRTL model for the binary system were obtained by calculating equilibrium compositions of the liquid and vapor phase with the experimental equilibrium temperatures, pressures and feed compositions. Moreover, (vapor + liquid) equilibrium data for the binary system were predicted by use of the UNIFAC model. Predicted results were compared with those from the ebulliometric method, and showed good agreement.

Liquid−Liquid Equilibria of Poly(ethylene glycol) 2000 + Sodium Citrate + Water at (25, 30, 35, 40, and 45) °C

The effect of temperature on the liquid−liquid equilibrium for the aqueous two-phase system containing poly(ethylene glycol) 2000 + sodium citrate + water was studied at (25, 30, 35, 40, and 45) °C. An equation for the binodal curves was obtained in terms of the concentrations of PEG 2000 and sodium citrate, and the temperature effect was also incorporated into the equation parameters. The tie lines were correlated using the Othmer−Tobias and Bancraft equations as well as osmotic virial equation. The mean deviations between the experimental and calculated equilibrium compositions in the top and bottom phases were <1 %.

Gas-Phase Kinetic Modeling of the AlCl3 Decomposition in the AlCl3-CO2-H2-HCl System for a Hot-Wall CVD Reactor

For a specific set of conditions applied in experimental hot-wall reactor investigations for depositing from precursor gas mixtures containing , kinetic modelling of the gas-phase reactions was carried out on the basis of rate parameters collected or estimated by Catoire and Swihart. Calculations are presented for upward flow rates of 200, 20, 0.41, and , a vertical tube reactor ( id) with a isothermal zone and with varying concentrations of , , , and HCl in the feed gas at a total pressure of . The residence times of the gas in the isothermal zone were 0.1, 1, 48, and . The results show that decomposes by reacting with and to form AlOCl as the major intermediate species. The water-gas shift reaction, , is found to take place very slowly at short residence times and much faster at higher ones. The generation increases with the AlOCl content in the gas phase. A comparison of the kinetic values with calculated equilibrium compositions shows that for residence times typically used in technical equipment for chemical vapor deposition (CVD), the gas-phase reactions are kinetically controlled at the temperature and pressure selected. The results may be helpful in understanding the complex reaction mechanisms involved in high-temperature CVD of alumina.

Isobaric vapor–liquid equilibria of the binary system maleic anhydride and di- n-butyl phthalate at 2.67, 5.33 and 8.00 kPa

Isobaric vapor–liquid equilibrium (VLE) data for the binary system maleic anhydride (MAN) + di- n-butyl phthalate (DBP) at 2.67, 5.33 and 8.00 kPa were determined using the ebulliometric method. The parameters of the NRTL model for the binary system were obtained by calculating equilibrium compositions of the liquid and vapor phase with the experimental equilibrium temperatures, pressures and feed compositions. Moreover, VLE data for the binary system were predicted by use of the UNIFAC model. Predicted results were compared with those from the ebulliometric method, and showed good agreement.

Surface tension of quantum fluids from molecular simulations.

We present the first molecular simulations of the vapor-liquid surface tension of quantum liquids. The path integral formalism of Feynman was used to account for the quantum mechanical behavior of both the liquid and the vapor. A replica-data parallel algorithm was implemented to achieve good parallel performance of the simulation code on at least 32 processors. We have computed the surface tension and the vapor-liquid phase diagram of pure hydrogen over the temperature range 18-30 K and pure deuterium from 19 to 34 K. The simulation results for surface tension and vapor-liquid orthobaric densities are in very good agreement with experimental data. We have computed the interfacial properties of hydrogen-deuterium mixtures over the entire concentration range at 20.4 and 24 K. The calculated equilibrium compositions of the mixtures are in excellent agreement with experimental data. The computed mixture surface tension shows negative deviations from ideal solution behavior, in agreement with experimental data and predictions from Prigogine's theory. The magnitude of the deviations at 20.4 K are substantially larger from simulations and from theory than from experiments. We conclude that the experimentally measured mixture surface tension values are systematically too high. Analysis of the concentration profiles in the interfacial region shows that the nonideal behavior can be described entirely by segregation of H(2) to the interface, indicating that H(2) acts as a surfactant in H(2)-D(2) mixtures.

Synthesis of purified AlN nano powder by transferred type arc plasma

Nano powder of aluminium nitride (AlN) is one of the materials necessary for developing solid insulating materials with high thermal conductivities. This paper describes the results of chemical equilibrium composition calculations and the results of experiments in synthesizing AlN nano powder using transferred type arc plasma. In order to increase the AlN content in synthesized powder, ammonia was recommended as a reacting/quenching gas, to be blown into aluminium gas in a temperature range between 2000 and 2400 K. The AlN content increased by more than 99% on passing the synthesized powder through ethanol.

Equilibrium concentrations for pyruvate dehydrogenase and the citric acid cycle at specified concentrations of certain coenzymes

It is of interest to calculate equilibrium compositions of systems of biochemical reactions at specified concentrations of coenzymes because these reactants tend to be in steady states. Thermodynamic calculations under these conditions require the definition of a further transformed Gibbs energy G″ by use of a Legendre transform. These calculations are applied to the pyruvate dehydrogenase reaction plus the citric acid cycle, but steady-state concentrations of CoA, acetyl-CoA and succinyl-CoA cannot be specified because they are involved in the conservation of carbon atoms. These calculations require the use of linear algebra to obtain further transformed Gibbs energies of formation of reactants and computer programs to calculate equilibrium compositions. At specified temperature, pH, ionic strength and specified concentrations of several coenzymes, the equilibrium composition depends on the specified concentrations of the coenzymes and the initial amounts of reactants.

Equilibrium concentrations for pyruvate dehydrogenase and the citric acid cycle at specified concentrations of certain coenzymes

It is of interest to calculate equilibrium compositions of systems of biochemical reactions at specified concentrations of coenzymes because these reactants tend to be in steady states. Thermodynamic calculations under these conditions require the definition of a further transformed Gibbs energy G ″ by use of a Legendre transform. These calculations are applied to the pyruvate dehydrogenase reaction plus the citric acid cycle, but steady-state concentrations of CoA, acetyl-CoA and succinyl-CoA cannot be specified because they are involved in the conservation of carbon atoms. These calculations require the use of linear algebra to obtain further transformed Gibbs energies of formation of reactants and computer programs to calculate equilibrium compositions. At specified temperature, pH, ionic strength and specified concentrations of several coenzymes, the equilibrium composition depends on the specified concentrations of the coenzymes and the initial amounts of reactants.